US4024132A - Azomethine pigments - Google Patents
Azomethine pigments Download PDFInfo
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- US4024132A US4024132A US05/693,388 US69338876A US4024132A US 4024132 A US4024132 A US 4024132A US 69338876 A US69338876 A US 69338876A US 4024132 A US4024132 A US 4024132A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B55/00—Azomethine dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B26/00—Hydrazone dyes; Triazene dyes
- C09B26/02—Hydrazone dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/04—Isoindoline dyes
Definitions
- A denotes an isocyclic or heterocyclic aromatic radical
- R denotes a H atom, an alkyl group containing 1-6 C atoms, or an aryl radical
- X 2 and X 4 denote H atoms or halogen atoms
- X 1 and X 3 denote H atoms or halogen atoms, alkoxy or alkylmercapto groups containing 1-6 C atoms, cycloalkoxy groups containing 5-6 C atoms, or aralkoxy, aryloxy or arylmercapto groups, it being possible for one of the substituents X 1 -X 4 also to be a nitro group, are obtained if
- Azomethine pigments of particular interest are those of the formula ##STR9## wherein M denotes a divalent metal atom and A, R and X 1 -X 4 have the meaning indicated, and particularly those of the formula ##STR10## wherein A 1 denotes a benzene, pyridine, pyrimidine or pyrane radical which can also contain a fused benzene nucleus, or denotes a pyrazolone radical, M 1 denotes a copper or nickel atom, X 5 to X 8 have the meaning indicated and R 1 denotes a hydrogen atom or the methyl group.
- Azomethine pigments which are particularly preferred are those of the formula ##STR11## wherein R 1 , M 1 and X 5 to X 8 have the meaning indicated above, Y 3 and Y 4 denote H atoms or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, nitro groups or groups of the formula ##EQU1## wherein M 2 denotes a Ca, Sr, Ba or Mn atom, and Z represents an O atom or an imino group, and particularly those of the formula ##STR12## wherein Z 3 denotes a hydroxyl or methyl group, and R 1 , M 1 , X 5 to X 8 , Y 3 and Y 4 have the meaning indicated above.
- Azomethine pigments of particular interest are also those of the formula ##STR13## wherein M 1 and X 5 to X 8 have the meaning indicated above, Y 1 denotes a H atom, a carboxyl group, a carbamoyl group, an alkoxycarbonyl or alkylcarbamoyl group containing 2-6 C atoms, a phenylcarbamoyl group which is optionally substituted in the phenyl radical by halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, or by trifluoromethyl groups, or a group of the formula ##EQU2## wherein M 2 has the meaning indicated above, and Y 2 denotes a H atom or halogen atom, an alkoxy group containing 1-4 C atoms, a nitro group or a nitrile group, those of the formula ##STR14## wherein R 2 denotes an alkyl group of 1-4 C-atoms, preferably
- the isoindolinone hydrazones used as starting materials are obtained by reacting hydrazine with an isoindolinone of the formula ##STR19## particularly an isoindolinone of the formula ##STR20## X 1 -X 8 and V in the formulae indicated having the indicated meaning.
- X 5 to X 8 denote chlorine atoms or hydrogen atoms
- those wherein X 5 and X 7 denote alkoxy, cycloalkoxy, aralkoxy, aryloxy, alkylthio or arylthio groups and X 6 and X 8 denote chlorine atoms can be obtained by reacting an ammonium salt or ester of tetrachloro-o-cyanobenzoic acid in a hydrophilic organic solvent with a compound of the formula X 5 M 3 wherein X 5 has the meaning indicated above and M 3 denotes an alkali metal atom, and esterifying the product obtained, if necessary.
- isoindolinones may be mentioned: 3,3-Dimethoxy-4,5,6,7-tetrachloro-isoindolinone, 3,3-dimethoxy-4,5,6,7-tetrabromo-isoindolinone, 3,3,6-trimethoxy-4,5,7-trichloro-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-butoxy-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-phenoxy-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-(p-chlorophenoxy)-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-(o-methylphenoxy)-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-methylmercapto-isoindolinone, 3,3-dimethoxy-4,5,
- hydrazones of the isoindolinones mentioned are condensed with compounds of the formula ##STR22## wherein Q denotes an O atom or an imino group, for example a phenylimino group, especially with aldehydes of the formula ##STR23## A and R in the formula indicated having the abovementioned meaning.
- Aldehydes or ketones of particular interest are those of the formula ##STR24## wherein R 1 denotes a hydrogen atom or the methyl group, and Y 3 , Y 4 and Z have the meaning indicated, and especially the hydroxyquinoline aldehydes of the formula ##STR25## wherein R 1 , Y 3 , Y 4 and Z 3 have the meaning indicated.
- Aldehydes of particular interest are also those of the following formulae ##STR26## wherein R 3 denotes a nitrile or carbamoyl group and R 2 denotes a lower alkyl group or an aryl group, ##STR27## wherein R 4 has the same meaning as R 3 , ##STR28## wherein Y 3 and Y 4 have the meaning indicated above and R 5 denotes a H atom, a lower alkyl group or an aryl group, hydroxynaphthaldehydes of the formula ##STR29## wherein Y 1 and Y 2 have the meaning indicated above, or pyrazolone aldehydes of the formula ##STR30## wherein R 6 , Y 5 and Y 6 have the meaning indicated above.
- aldehydes or ketones may be mentioned as examples:
- the starting materials used are appropriately, on the one hand, isoindolinones of the formula 20), particularly those of the formula 21), and, on the other hand, hydrazones of the aldehydes or ketones of the formulae 22-29).
- the condensation of the hydrazone with the oxo compound or the isoindolinone is appropriately carried out in water or an organic solvent, at an elevated temperature, preferably between 50° C and the boiling point of the solvent used.
- solvents may be mentioned: water, alcohol, glacial acetic acid, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, butyrolactone, glycol monomethyl ether, xylene, chlorobenzene, o-dichlorobenzene, nitrobenzene or mixtures thereof.
- azomethines are sparingly soluble in the solvents mentioned, they can be isolated easily by filtration. Impurities which may be present can be removed by washing.
- the azomethines obtained are treated with agents which donate divalent metals, for example with salts of zinc, manganese, cobalt or iron, but particularly of copper and nickel, or of mixtures of such metals.
- agents which donate divalent metals for example with salts of zinc, manganese, cobalt or iron, but particularly of copper and nickel, or of mixtures of such metals.
- the formates, acetates or stearates of these metals are preferably used.
- the metallisation is appropriately carried out in one of the abovementioned solvents.
- the metallisation can also be carried out at the same time as the condensation, by condensing the aldehyde together with the hydrazone in one of the abovementioned solvents, in the presence of metal salts.
- the metal complexes often additionally contain 0.5-2 mols of water of crystallisation, which, in appropriate instances, exerts a slight influence on the shade of the colorant obtained.
- the new colorants represent valuable pigments which can be used, in a finely dispersed form, for pigmenting high molecular organic material, for example cellulose ethers and esters, such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, such as polymerisation resins or condensation resins, for example aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride, polyethylene or polypropylene, polyacrylonitrile, polyacrylic acid esters, polyamides, polyurethanes or polyesters, rubber, casein, silicone and silicone resins, individually or as mixtures.
- cellulose ethers and esters such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate
- natural resins or synthetic resins such as
- the resulting colorations are distinguished by good fastness to light and migration.
- a colorant having similar properties is obtained if 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine is used as the starting material.
- the yield is 75% of theory.
- the bishydrazones described in Examples 1 - 30 can also be prepared by a known method from the cyanobenzoic acid esters and the corresponding monohydrazones.
- the bishydrazones of the following formula are obtained analogously if a 4,6-dihydroxypyrimidine-5-N-phenylaldimine is used instead of 2,4-dihydroxyquinoline-3-N-phenylaldimine in the process of Example 33.
- the bishydrazones of the formula which follows are prepared by a known method from the cyanobenzoic acid esters and the corresponding monohydrazones of 3-hydroxy-isoquinolone-4-aldehyde. The meaning of the symbols is given in the table.
- the metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Example 1 with the corresponding metal salts ##STR72##
- the barium salt of the copper complex of Example 199 is prepared by the process of Example 200.
- a pigment is obtained which colours PVC in greenish-tinged yellow shades of good fastness to light and migration.
- the nickel complex of the same colorant is prepared by the process of Example 200. It colours PVC in yellow shades of good fastness to light and migration.
- the metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Examples 56 and 57, with the corresponding metal salts. ##STR75##
- the metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Examples 50-55 with the corresponding metal salts. ##STR77##
- the metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 64-67 with the corresponding metal salts.
- the metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 68-70 with the corresponding metal salts.
- the metal complexes of the following formula are obtained by reacting the bishydrazones of the Examples under 1 with the corresponding metal salts.
- All the metal complexes described can also be prepared directly from the components, isoindolinone-3-ylidene hydrazine, hydroxy-aldehyde or hydroxy-ketone and metal salt by the one-pot method.
- the formation of the metal complex can also be carried out in, for example, dimethylformamide, methylcellosolve, ethylcellosolve, Carbitol and glycol, instead of glacial acetic acid.
- the pigment is also suitable for other printing processes, such as gravure printing, offset printing and flexographic printing, and here too gives very good results.
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Abstract
Azomethine pigments of the formula ##STR1## and metal complexes thereof, wherein A denotes an isocyclic or heterocyclic aromatic radical, R denotes a H atom, an alkyl group containing 1-6 C atoms, or an aryl radical, X2 and X4 denote H atoms or halogen atoms, X1 and X3 denote H atoms or halogen atoms, alkoxy or alkylmercapto groups containing 1-6 C atoms, cycloalkoxy groups containing 5-6 C atoms, or aralkoxy, aryloxy or arylmercapto groups, it being possible for one of the substituents X1 -X4 also to be a nitro group which are useful for pigmenting of high molecular material.
Description
This is a division of application Ser. No. 502,246, filed on Aug. 30, 1974, now U.S. Pat. No. 3,974,149.
It has been found that new, valuable azomethine pigments of the formula ##STR2## wherein A denotes an isocyclic or heterocyclic aromatic radical, R denotes a H atom, an alkyl group containing 1-6 C atoms, or an aryl radical, X2 and X4 denote H atoms or halogen atoms, X1 and X3 denote H atoms or halogen atoms, alkoxy or alkylmercapto groups containing 1-6 C atoms, cycloalkoxy groups containing 5-6 C atoms, or aralkoxy, aryloxy or arylmercapto groups, it being possible for one of the substituents X1 -X4 also to be a nitro group, are obtained if
A. AN ISOINDOLINONE HYDRAZONE OF THE FORMULA ##STR3## particularly an isoindolinone hydrazone of the formula ##STR4## wherein X5 and X7 denote H atoms or chlorine atoms or alkoxy groups containing 1-4 C atoms, X6 and X8 denote H atoms or chlorine atoms, X6 and X8 representing chlorine atoms if X5 and X7 denote alkoxy groups, is condensed with a compound of the formula ##STR5## wherein Q denotes an O atom or an imino group, or
b. an isoindolinone of the formula ##STR6## wherein V denotes a group of the formula ##STR7## wherein Z1 denotes an imino or thio group and the Z2 's denote halogen atoms, or alkoxy or secondary amino groups, is condensed with a hydrazone of the formula ##STR8## and the resulting azomethine is optionally metallised.
Azomethine pigments of particular interest are those of the formula ##STR9## wherein M denotes a divalent metal atom and A, R and X1 -X4 have the meaning indicated, and particularly those of the formula ##STR10## wherein A1 denotes a benzene, pyridine, pyrimidine or pyrane radical which can also contain a fused benzene nucleus, or denotes a pyrazolone radical, M1 denotes a copper or nickel atom, X5 to X8 have the meaning indicated and R1 denotes a hydrogen atom or the methyl group.
Azomethine pigments which are particularly preferred are those of the formula ##STR11## wherein R1, M1 and X5 to X8 have the meaning indicated above, Y3 and Y4 denote H atoms or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, nitro groups or groups of the formula ##EQU1## wherein M2 denotes a Ca, Sr, Ba or Mn atom, and Z represents an O atom or an imino group, and particularly those of the formula ##STR12## wherein Z3 denotes a hydroxyl or methyl group, and R1, M1, X5 to X8, Y3 and Y4 have the meaning indicated above.
Azomethine pigments of particular interest are also those of the formula ##STR13## wherein M1 and X5 to X8 have the meaning indicated above, Y1 denotes a H atom, a carboxyl group, a carbamoyl group, an alkoxycarbonyl or alkylcarbamoyl group containing 2-6 C atoms, a phenylcarbamoyl group which is optionally substituted in the phenyl radical by halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, or by trifluoromethyl groups, or a group of the formula ##EQU2## wherein M2 has the meaning indicated above, and Y2 denotes a H atom or halogen atom, an alkoxy group containing 1-4 C atoms, a nitro group or a nitrile group, those of the formula ##STR14## wherein R2 denotes an alkyl group of 1-4 C-atoms, preferably a methyl group, or an optionally substituted aryl group, those of the formula ##STR15## wherein R3 denotes a nitrile or carbamoyl group, those of the formula ##STR16## wherein R4 denotes a nitrile or carbamoyl group, those of the formula ##STR17## wherein R5 denotes a H atom, an alkyl group containing 1-4 C atoms, or an aryl group, or those of the formula ##STR18## wherein M1 and X5 to X8 have the meaning indicated above and R6 denotes an alkyl group containing 1-4 C atoms, an alkoxycarbonyl group containing 2-5 C atoms, a carboxyl group, a carbamoyl group or a group of the formula ##EQU3## wherein M2 denotes a Ca, Sr, Ba or Mn atom, and Y5 and Y6 denote H atoms or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, nitro, acylamino, carbamoyl or sulphamoyl groups or groups of the formula ##EQU4## wherein M2 denotes a Ca, Sr, Ba or Mn atom.
The isoindolinone hydrazones used as starting materials are obtained by reacting hydrazine with an isoindolinone of the formula ##STR19## particularly an isoindolinone of the formula ##STR20## X1 -X8 and V in the formulae indicated having the indicated meaning.
It is preferable to start from 3-imino-isoindolinone or from 3,3'-dialkoxy-iminoisoindolinones of the formula ##STR21## wherein X5 to X8 have the meaning indicated and R3 denotes an alkyl group containing 1-4 C atoms. Those starting materials wherein X5 to X8 denote chlorine atoms or hydrogen atoms, are known, and those wherein X5 and X7 denote alkoxy, cycloalkoxy, aralkoxy, aryloxy, alkylthio or arylthio groups and X6 and X8 denote chlorine atoms, can be obtained by reacting an ammonium salt or ester of tetrachloro-o-cyanobenzoic acid in a hydrophilic organic solvent with a compound of the formula X5 M3 wherein X5 has the meaning indicated above and M3 denotes an alkali metal atom, and esterifying the product obtained, if necessary.
The following examples of isoindolinones may be mentioned: 3,3-Dimethoxy-4,5,6,7-tetrachloro-isoindolinone, 3,3-dimethoxy-4,5,6,7-tetrabromo-isoindolinone, 3,3,6-trimethoxy-4,5,7-trichloro-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-butoxy-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-phenoxy-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-(p-chlorophenoxy)-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-(o-methylphenoxy)-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-methylmercapto-isoindolinone, 3,3-dimethoxy-4,5,7-trichloro-6-ethylmercapto-isoindolinone, 3,3,4,6-tetramethoxy-5,7-dichloro-isoindolinone and 3-imino-isoindolinone.
The hydrazones of the isoindolinones mentioned are condensed with compounds of the formula ##STR22## wherein Q denotes an O atom or an imino group, for example a phenylimino group, especially with aldehydes of the formula ##STR23## A and R in the formula indicated having the abovementioned meaning.
Aldehydes or ketones of particular interest are those of the formula ##STR24## wherein R1 denotes a hydrogen atom or the methyl group, and Y3, Y4 and Z have the meaning indicated, and especially the hydroxyquinoline aldehydes of the formula ##STR25## wherein R1, Y3, Y4 and Z3 have the meaning indicated.
Aldehydes of particular interest are also those of the following formulae ##STR26## wherein R3 denotes a nitrile or carbamoyl group and R2 denotes a lower alkyl group or an aryl group, ##STR27## wherein R4 has the same meaning as R3, ##STR28## wherein Y3 and Y4 have the meaning indicated above and R5 denotes a H atom, a lower alkyl group or an aryl group, hydroxynaphthaldehydes of the formula ##STR29## wherein Y1 and Y2 have the meaning indicated above, or pyrazolone aldehydes of the formula ##STR30## wherein R6, Y5 and Y6 have the meaning indicated above. In the above formulae 22 to 29, the aldehyde group can also be replaced by an azomethine group of the formula --CR1 =Q or --CH=Q wherein Q preferably denotes the phenylimino group.
The following aldehydes or ketones may be mentioned as examples:
1. o-Hydroxybenzaldehydes
Salicylaldehyde, 4-chloro-2-hydroxybenzaldehyde, 5-chloro-2-hydroxybenzaldehyde, 3-nitro-2-hydroxybenzaldehyde, 5-nitro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 3,5-dibromo-2-hydroxybenzaldehyde, 5-phenylazo-2-hydroxybenzaldehyde, 5-(2'-chloro-phenylazo)-2-hydroxybenzaldehyde, 5-(2',5'-dichlorophenylazo)-2-hydroxybenzaldehyde, 5-(2'-methyl-phenylazo)-2-hydroxybenzaldehyde, 5-(2'-methoxy-phenylazo)-2-hydroxybenzaldehyde, 5-(2'-methoxy-4'-nitro-phenylazo)-2-hydroxybenzaldehyde and 5-(2'-methoxy-5'-carbamoyl-phenylazo)-2-hydroxybenzaldehyde.
2. Hydroxynaphthaldehydes
2-Hydroxynaphthaldehyde, 6-bromo-2-hydroxynaphthaldehyde, 5-nitro-2-hydroxynaphthaldehyde, 2-hydroxy-3-carboxy-naphthaldehyde, 2-hydroxy-3-methoxycarbonyl-naphthaldehyde, 2-hydroxy-3-phenylcarbamoyl-naphthaldehyde, 2-hydroxy-3-(4'-chlorophenylcarbamoyl)naphthaldehyde, 2-hydroxy-3-(4'-chloro-2'-methylphenylcarbamoyl-naphthaldehyde, 2-hydroxy-3-(2',5'-dimethoxy-3'-chloro-phenylcarbamoyl-naphthaldehyde, 2-hydroxy-6-bromo-3-carboxynaphthaldehyde and 2-hydroxy-6-bromo-3-phenylcarbamoylnaphthaldehyde.
3. Heterocyclic aldehydes and ketones
2,6-Dihydroxy-4-methyl-5-cyano-3-pyridine aldehyde, 2,6-dihydroxy-4-methyl-5-carboxy-3-pyridine aldehyde, 2,6-dihydroxy-4-methyl-5-carbamoyl-3-pyridine aldehyde, 2,4-dihydroxy-3-quinoline aldehyde, 5-chloro-2,4-dihydroxy-3-quinoline aldehyde, 6-chloro-2,4-dihydroxy-3-quinoline aldehyde, 7-chloro-2,4-dihydroxy-3-quinoline aldehyde, 8-chloro-2,4-dihydroxy-3-quinoline aldehyde, 6,8-dichloro-2,4-dihydroxy-3-quinoline aldehyde, 7,8-dichloro-2,4-dihydroxy-3-quinoline aldehyde, 6-methyl-2,4-dihydroxy-3-quinoline aldehyde, 7-methyl-2,4-dihydroxy-3-quinoline aldehyde, 8-methyl-2,4-dihydroxy-3-quinoline aldehyde, 6-chloro-8-methyl-2,4-dihydroxy-3-quinoline aldehyde, 2,4-dihydroxy-3-acetyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methyl-quinoline, 2,4-dihydroxy-3-acetyl-6-chloro-quinoline, 3-hydroxy-4-isoquinolone aldehyde, N-methyl-3-hydroxy-4-isoquinoline aldehyde, N-phenyl-3-hydroxy-4-isoquinoline aldehyde, N-naphthyl-3-hydroxy-4-isoquinolone aldehyde, 2-methyl-4,6-dihydroxy-5-pyrimidine aldehyde, 2-phenyl-4,6-dihydroxy-5-pyrimidine aldehyde, 4-hydroxy-3-quinaldine aldehyde, 6-chloro-4-hydroxy-3-quinaldine aldehyde, 6-methoxy-4-hydroxy-3-quinaldine aldehyde and further aldehydes.
4-Hydroxycoumarin-3-aldehyde, 1-phenyl-3-methyl-4-formylpyrazolone- 5,1-phenyl-3-carboxy-4-formylpyrazolone-5,1-phenyl-3-methoxycarbonyl-4-formylpyrazolone- 5,1-phenyl-3-ethoxycarbonyl-4-formylpyrazolone- 5,1-(2'-chlorophenyl)-3-methyl-4-formylpyrazolone- 5,1-(4'-chlorophenyl)-3-methyl-4-formylpyrazolone- 5,1-(2'-methylphenyl)-3-methyl-4-formylpyrazolone-5 and 1-(4'-methylphenyl)-3-methyl-4-formylpyrazolone-5.
Instead of the aldehydes or ketones, it is also possible to use imines, particularly phenylimines, thereof.
For the embodiment (b) of the process according to the invention, the starting materials used are appropriately, on the one hand, isoindolinones of the formula 20), particularly those of the formula 21), and, on the other hand, hydrazones of the aldehydes or ketones of the formulae 22-29).
The condensation of the hydrazone with the oxo compound or the isoindolinone is appropriately carried out in water or an organic solvent, at an elevated temperature, preferably between 50° C and the boiling point of the solvent used. The following examples of solvents may be mentioned: water, alcohol, glacial acetic acid, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, butyrolactone, glycol monomethyl ether, xylene, chlorobenzene, o-dichlorobenzene, nitrobenzene or mixtures thereof.
As the resulting azomethines are sparingly soluble in the solvents mentioned, they can be isolated easily by filtration. Impurities which may be present can be removed by washing.
For conversion into the metal complexes, the azomethines obtained are treated with agents which donate divalent metals, for example with salts of zinc, manganese, cobalt or iron, but particularly of copper and nickel, or of mixtures of such metals. The formates, acetates or stearates of these metals are preferably used. The metallisation is appropriately carried out in one of the abovementioned solvents.
The metallisation can also be carried out at the same time as the condensation, by condensing the aldehyde together with the hydrazone in one of the abovementioned solvents, in the presence of metal salts.
The metal complexes often additionally contain 0.5-2 mols of water of crystallisation, which, in appropriate instances, exerts a slight influence on the shade of the colorant obtained.
The new colorants represent valuable pigments which can be used, in a finely dispersed form, for pigmenting high molecular organic material, for example cellulose ethers and esters, such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, such as polymerisation resins or condensation resins, for example aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride, polyethylene or polypropylene, polyacrylonitrile, polyacrylic acid esters, polyamides, polyurethanes or polyesters, rubber, casein, silicone and silicone resins, individually or as mixtures.
It is immaterial here whether the high molecular compounds mentioned are present as plastic compositions or melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the application, it is found to be advantageous to use the new pigments as toners or in the form of preparations.
The resulting colorations are distinguished by good fastness to light and migration.
In the following examples, unless otherwise specified, the parts denote parts by weight, and the percentages denote percentages by weight.
119.6 g of 3,4,5,6-tetrachloro-2-cyanobenzoic acid methyl ester are dissolved in 600 ml of methanol and 70.6 g of a 30.6% strength methanolic solution of Na methylate. The solution is cooled to 10° C and is added dropwise at 10° C to a solution of 200 ml of hydrazine hydrate in 400 ml of methanol. A yellowish precipitate is formed. The reaction mixture is stirred at room temperature for 2 hours and is then warmed to 35° C over the course of 30 minutes and 200 ml of glacial acetic acid are added at this temperature. After stirring for 1 hour at room temperature, the product is filtered off and the filter residue is washed with methanol and water. The material filtered off is then extracted by boiling in 1 l of methylcellosolve for a further 2 hours, filtered off at room temperature and washed with methylcellosolve and methanol. After drying at 70° C, 98 g (82% of theory) of analytically pure 4,5,6,7-tetrachloro-isoindolin-1-on- 3-ylidene hydrazine of the formula ##STR31## are obtained.
In an analogous manner, 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine is obtained in 87% yield from 4,6-dichloro-3,5-dimethoxy-2-cyanobenzoic acid methyl ester, 4,5,7-trichloro-6-methoxy-isoindolin-1-ylidene-3-hydrazine is obtained in 91% yield from 3,5,6-trichloro-4-methoxy-2-cyanobenzoic acid methyl ester and 4,5,7-trichloro-6-phenoxy-isoindolin-1-on-3-ylidene hydrazine is obtained in 67% yield from 3,4,6-trichloro-5-phenoxy-2-cyanobenzoic acid methyl ester.
4.49 g of tetrachloro-isoindolin-1-ylidene-3-hydrazine and 4.36 g of 1-formyl-2-hydroxy-3-naphthoic acid anilide in 250 ml of methylcellosolve are heated under reflux for 30 minutes. The thick, yellow precipitate is filtered off at 80° C, washed well with methylcellosolve, alcohol and acetone and dried at 80° C. 8.3 g (97% of theory) of the analytically pure colorant of the formula ##STR32## are obtained. Instead of methylcellosolve, Carbitols, dimethylformamide or glacial acetic acid can also be used.
The azomethines of the following formula ##STR33## wherein the symbols have the meaning indicated in the following table, are obtained by an analogous process.
Table I
__________________________________________________________________________
Example
No. X.sub.1
X.sub.2
X.sub.3
X.sub.4
Y.sub.1 Y.sub.2
R Shade
Yield
__________________________________________________________________________
2 Cl Cl
Cl Cl
H H H yellow
94%
3 Cl Cl
Cl Cl
COOH H H yellow
78%
4 Cl Cl
Cl Cl
##STR34## H H orange
74%
5 Cl Cl
Cl Cl
COOH Br
H yellow
75%
6 CH.sub.3 O
Cl
CH.sub.3 O
Cl
COOH H H yellow
87%
7 CH.sub.3 O
Cl
CH.sub.3 O
Cl
COOH Br
H yellow
89%
8 CH.sub.3 O
Cl
CH.sub.3 O
Cl
H H H yellow
87%
9 CH.sub.3 O
Cl
CH.sub.3 O
Cl
##STR35## H H yellow
90%
__________________________________________________________________________
5.98 g of 4,5,6,7-tetrachloroisoindolin-1-on-3-ylidene hydrazine and 3.78 g of 2,4-dihydroxy-quinoline-3-aldehyde in glacial acetic acid are boiled under reflux for 5 minutes. The yellow precipitate is filtered off at room temperature, washed well with glacial acetic acid, alcohol and acetone and dried at 80° C. 8.2 g (87% of theory) of the analytically pure pigment of the formula ##STR36## are obtained. The hydrazones of the following formula ##STR37## wherein the symbols have the meaning indicated in Table II which follows, are obtained by an analogous process.
Table II
__________________________________________________________________________
Example
No. X.sub.1
X.sub.2
X.sub.3
X.sub.4
Y.sub.7
Y.sub.8
Y.sub.9
Y.sub.10
R Shade
Yield
__________________________________________________________________________
11 Cl Cl
Cl Cl
H Cl H H H yellow
95%
12 Cl Cl
Cl Cl
H CH.sub.3
H H H yellow
92%
13 Cl Cl
Cl Cl
H H Cl Cl H yellow
90%
14 Cl Cl
Cl Cl
Cl
H H Cl H yellow
67%
15 Cl Cl
Cl Cl
H H H H CH.sub.3
yellow
77%
16 Cl Cl
OCH.sub.3
Cl
H H H H H yellow
86%
17 Cl Cl
OCH.sub.3
Cl
H Cl H H H yellow
91%
18 OCH.sub.3
Cl
OCH.sub.3
Cl
H H H H H yellow
78%
19 OCH.sub.3
Cl
OCH.sub.3
Cl
H CH.sub.3
H H H yellow
92%
20 OCH.sub.3
Cl
OCH.sub.3
Cl
H Cl H H H yellow
85%
21 Cl Cl
Cl Cl
H Cl H H CH.sub.3
yellow
81%
22 Cl Cl
Cl Cl
H CH.sub.3
H H CH.sub.3
yellow
67%
23 OCH.sub.3
Cl
OCH.sub.3
Cl
H H H H CH.sub.3
yellow
91%
24 OCH.sub.3
Cl
OCH.sub.3
Cl
H Cl H H CH.sub.3
yellow
82%
25 OCH.sub.3
Cl
OCH.sub.3
Cl
H CH.sub.3
H H CH.sub.3
yellow
93%
26 OCH.sub.3
Cl
OCH.sub.3
Cl
H H H H H yellow
91%
27 Cl Cl
Cl Cl
H H Cl Cl CH.sub.3
yellow
82%
28 Cl Cl
CH.sub.3 O
Cl
H H H H CH.sub.3
yellow
87%
29 CH.sub.3 O
Cl
CH.sub.3 O
Cl
H H Cl Cl CH.sub.3
yellow
97%
30 CH.sub.3 O
Cl
CH.sub.3 O
Cl
H H Cl Cl H yellow
91%
31 Cl Cl
PhO Cl
H H H H CH.sub.3
yellow
87%
32 Cl Cl
PhO Cl
H H H H H yellow
94%
__________________________________________________________________________
14.50 g of 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine and 13.2 g of 2,4-dihydroxyquinoline-3-N-phenylaldimine in 250 ml of methylcellosolve are boiled under reflux for 1 hour. The yellow precipitate is filtered off at 100° C, washed well with alcohol and dried at 80° C (under vacuum). 18.75 g (82% of theory) of the analytically pure bishydrazine are obtained.
The following hydrazones, for example, are obtained by an analogous process:
Table III
__________________________________________________________________________
Example
No. X.sub.1
X.sub.2
X.sub.3
X.sub.4
Y.sub.7
Y.sub.8
Y.sub.9
Y.sub.10
R Shade
Yield
__________________________________________________________________________
34 Cl Cl
Cl Cl
H Cl
H H CH.sub.3
yellow
72%
35 CH.sub.3 O
Cl
CH.sub.3 O
Cl
H Cl
H H CH.sub.3
yellow
82%
__________________________________________________________________________
10.95 g of imino-isoindolinone hydrochloride and 12.18 g of the hydrazone of 2,4-dihydroxyquinoline-3-aldehyde are boiled for 5 minutes with 99 g of sodium acetate in 250 ml of glacial acetic acid. The yellow suspension is filtered at 80° C and the precipitate is washed well with glacial acetic acid, alcohol and acetone and dried at 80° C. 16.8 g (84% of theory) of the analytically pure bishydrazone are obtained.
The following bishydrazones, for example, are obtained by an analogous process:
Table IV
______________________________________
Ex.
No. X.sub.1
X.sub.2
X.sub.3
X.sub.4
Y.sub.7
Y.sub.8
Y.sub.9
Y.sub.10
R Shade Yield
______________________________________
37 H H H H H H H H CH.sub.3
yellow
75%
38 H H H H H Cl H H CH.sub.3
yellow
77%
______________________________________
5.98 g of 4,5,6,7-tetrachloroisoindolin-1-on-3-ylidene hydrazine and 4.04 g of 1-phenyl-3-methyl-4-formyl-pyrazolone-5 in 200 ml of alcohol are heated under reflux for one hour. The yellow suspension is filtered while warm and the filter residue is washed well with alcohol and dried at 80° C. 9.2 g (95% of theory) of the analytically pure pigment of the formula ##STR38## are obtained.
The hydrazones of the following formula ##STR39## wherein the symbols have the meaning indicated in Table V which follows, are obtained by an analogous process.
Table V
__________________________________________________________________________
Example
No. X.sub.1
X.sub.2
X.sub.3
X.sub.4
X.sub.5
Y.sub.6
R.sub.6
Shade
Yield
__________________________________________________________________________
40 Cl Cl
Cl Cl Cl H CH.sub.3
yellow
86%
41 OCH.sub.3
Cl
OCH.sub.3
Cl Cl H COOC.sub.2 H.sub.5
yellow
68%
42 Cl Cl
Cl Cl H H CH.sub.3
yellow
100%
43 CH.sub.3 O
Cl
CH.sub.3 O
Cl H CH.sub.3
CH.sub.3
yellow
100%
44 Cl Cl
Cl Cl H CH.sub.3
CH.sub.3
yellow
100%
45 CH.sub.3 O
Cl
CH.sub.3 O
Cl H H CONH.sub.2
yellow
73%
__________________________________________________________________________
15.00 g of 4,5,6,7-tetrachloroisoindolin-1-on-3-ylidene hydrazine and 13.25 g of the anil of 4-hydroxycoumarin-3-aldehyde are suspended in 350 ml of methylcellosolve and heated at 100° C for 1 hour. The resulting yellow precipitate is filtered off at room temperature, washed with methylcellosolve, alcohol and acetone and dried at 80° C. 22.3 g (95% of theory) of the colorant of the formula ##STR40## are obtained.
A colorant having similar properties is obtained if 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine is used as the starting material. The yield is 75% of theory.
The bishydrazones described in Examples 1 - 30 can also be prepared by a known method from the cyanobenzoic acid esters and the corresponding monohydrazones.
14.5 g of 5,7-trichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine are suspended in a finely dispersed form in 200 ml of methylcellosolve and heated to 70° C. 11.6 g of 1-phenyl-3-carboxy-4-formyl-pyrazolone-5 in 150 ml of methylcellosolve are added slowly to this suspension. The reaction mixture is then kept at 100° C for 2 hours. After cooling to room temperature, the yellow crystals precipitated are filtered off, washed with a little methylcellosolve, with alcohol and acetone and dried at 80° C. 14.7 g (59% of theory) of the analytically pure compound of the formula ##STR41## are obtained.
An analogous compound is obtained in 72% yield, if the instructions of Example 48 are followed, but the starting material is 4,5,6,7-tetrachloro-isoindolin-1-on-3-ylidene hydrazine.
The bishydrazones of the following formula are obtained if the process of Example 10 is followed, using 2-methyl-4-hydroxy-quinoline-3-aldehyde instead of 2,4-dihydroxyquinoline-3-aldehyde. ##STR42##
The meaning of the symbols is indicated in Table VI which follows.
Table VI
______________________________________
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
Y.sub.3
Shade Yield
______________________________________
50 Cl Cl Cl Cl H yellow 97%
51 CH.sub.3 O
Cl CH.sub.3 O
Cl H yellow 84%
52 Cl Cl Cl Cl OCH.sub.3
yellow 94%
53 CH.sub.3 O
Cl CH.sub.3 O
Cl CH.sub.3 O
yellow 89%
54 Cl Cl Cl Cl Cl yellow 94%
55 CH.sub.3 O
Cl CH.sub.3 O
Cl Cl yellow 92%
______________________________________
The bishydrazones of the formula which follows are obtained analogously if a 4,6-dihydroxypyrimidine-5-aldehyde is used instead of 2,4-dihydroxyquinoline-3-aldehyde in the process of Example 10. The meaning of the symbols is given in Table VII.
Table VII
______________________________________
##STR43##
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
R Shade Yield
______________________________________
56 Cl Cl Cl Cl CH.sub.3
yellow 84%
57 CH.sub.3 O
Cl CH.sub.3 O
Cl CH.sub.3
yellow 81%
______________________________________
The bishydrazones of the following formula are obtained analogously if a 4,6-dihydroxypyrimidine-5-N-phenylaldimine is used instead of 2,4-dihydroxyquinoline-3-N-phenylaldimine in the process of Example 33.
______________________________________
##STR44##
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
R Shade Yield
______________________________________
58 Cl Cl Cl Cl H yellow 78%
59 Cl Cl CH.sub.3 O
Cl H yellow 92%
60 CH.sub.3 O
Cl CH.sub.3 O
Cl H yellow 85%
61 Cl Cl Cl Cl CH.sub.3
yellow 86%
62 Cl Cl CH.sub.3 O
Cl CH.sub.3
yellow 85%
63 CH.sub.3 O
Cl CH.sub.3 O
Cl CH.sub.3
yellow 73%
______________________________________
The bishydrazones of the following formula are obtained analogously if a 2,6-dihydroxy-pyridine-5-aldehyde is used instead of 2,4-dihydroxyquinoline-3-aldehyde in the process of Example 10.
______________________________________
##STR45##
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
R Shade Yield
______________________________________
64 Cl Cl Cl Cl CN yellow 94%
65 CH.sub.3 O
Cl CH.sub.3 O
Cl CN yellow 86%
66 Cl Cl Cl Cl CONH.sub.2
yellow 73%
67 CH.sub.3 O
Cl CH.sub.3 O
Cl CONH.sub.2
yellow 68%
______________________________________
The bishydrazones of the following formula are obtained analogously if a benzimidazolo-6-hydroxypyridine-5-aldehyde is used instead of 2,4-dihydroxyquinoline-3-aldehyde in the process of Example 10
______________________________________
##STR46##
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
R Shade Yield
______________________________________
68 Cl Cl Cl Cl CN orange
92%
69 CH.sub.3 O
Cl CH.sub.3 O
Cl CN yellow
88%
70 CH.sub.3 O
Cl CH.sub.3 O
Cl CONH.sub.2
yellow
76%
______________________________________
The bishydrazones of the formula which follows are prepared by a known method from the cyanobenzoic acid esters and the corresponding monohydrazones of 3-hydroxy-isoquinolone-4-aldehyde. The meaning of the symbols is given in the table.
__________________________________________________________________________
##STR47##
Example
No. X.sub.1
X.sub.2
X.sub.3
X.sub.4
R Shade
Yield
__________________________________________________________________________
yellow-
71 Cl Cl Cl Cl H orange
68%
72 Cl Cl CH.sub.3 O
Cl H orange
91%
73 CH.sub.3 O
Cl CH.sub.3 O
Cl H yellow
80%
74 Cl Cl Cl Cl CH.sub.3 orange
75%
75 Cl Cl CH.sub.3 O
Cl CH.sub.3 yellow
90%
76 CH.sub.3 O
Cl CH.sub.3 O
Cl CH.sub.3 yellow
69%
77 Cl Cl Cl Cl
##STR48## yellow
87%
78 Cl Cl CH.sub.3 O
Cl
##STR49## yellow
90%
79 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR50## yellow
65%
80 Cl Cl Cl Cl
##STR51## yellow
89%
81 Cl Cl CH.sub.3 O
Cl
##STR52## yellow
90%
82 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR53## yellow
65%
83 Cl Cl Cl Cl
##STR54## yellow
87%
84 Cl Cl CH.sub.3 O
Cl
##STR55## yellow
86%
85 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR56## yellow
60%
86 Cl Cl Cl Cl
##STR57## orange
94%
87 Cl Cl CH.sub.3 O
Cl
##STR58## yellow
85%
88 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR59## orange
82%
__________________________________________________________________________
1.72 g of the bishydrazone from Example 1 are reacted, in 70 ml of methylcellosolve, with 0.83 g of Ni(ac)2.4H2 O for 4 hours at 90° C. The orange reaction product is filtered off while warm, washed well with methylcellosolve, alcohol and acetone and dried at 80° C. 1.65 g (87%) are obtained of an orange pigment of the formula ##STR60## which colours PVC in orange shades of good fastness to light and migration. The metallisation can also be carried out, for example, in dimethylformamide or Carbitol. The following metal complexes are prepared by an analogous process: ##STR61##
Table VIII
__________________________________________________________________________
Example
No. X.sub.1
X.sub.2
X.sub.3
X.sub.4
Y.sub.1 Y.sub.2
M Shade
__________________________________________________________________________
90 Cl Cl Cl Cl H H Cu orange
91 Cl Cl Cl Cl H H Zn orange
92 CH.sub.3 O
Cl CH.sub.3 O
Cl H H Ni orange
93 CH.sub.3 O
Cl CH.sub.3 O
Cl H H Cu brown
94 Cl Cl Cl Cl COOH H Ni orange
95 Cl Cl Cl Cl COOH H Zn orange
96 Cl Cl Cl Cl COOH H Cd yellow
97 CH.sub.3 O
Cl CH.sub.3 O
Cl COOH H Ni orange
98 CH.sub.3 O
Cl CH.sub.3 O
Cl COOH H Cu yellow
99 Cl Cl Cl Cl COOH Br Ni orange
100 Cl Cl Cl Cl COOH Br Cu yellow
101 CH.sub.3 O
Cl CH.sub.3 O
Cl COOH Br Ni yellow-
orange
102 CH.sub.3 O
Cl CH.sub.3 O
Cl COOH Br Cu yellow
103 Cl Cl Cl Cl
H Cu brown
104 Cl Cl Cl Cl
##STR62## H Zn orange
105 Cl Cl Cl Cl
##STR63## H Cu brown
106 Cl Cl Cl Cl
##STR64## H Zn orange
107 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR65## H Ni brown
108 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR66## H Cu brown
109 H H H H H H Ni yellow
110 H H H H H H Cu yellow
111 H H H H H H Co yellow-
brown
__________________________________________________________________________
1.48 g of the bishydrazone of Example 20 are reacted in 60 ml of methylcellosolve with 0.66 g of Cu(ac)2.H2 O for 3 hours at 90° C. The green-yellow reaction product is filtered off while warm, washed well with methylcellosolve, alcohol and acetone and dried at 100° C. 1.55 g (93%) are obtained of a greenish-tinged yellow pigment of the formula ##STR67## which colours PVC in greenish-tinged yellow shades of outstanding fastness to light and migration.
The metal complexes of the formula ##STR68## wherein the symbols have the meaning indicated in Table IX which follows are obtained by an analogous process.
Table IX
__________________________________________________________________________
Example
No. X.sub.1
X.sub.2
X.sub.3
X.sub.4
Y.sub.7
Y.sub.8
Y.sub.9
Y.sub.10
R M Shade
__________________________________________________________________________
113 Cl Cl
Cl Cl
H H H H H Ni yellow
114 Cl Cl
Cl Cl
H H H H H Cu yellow-green
115 Cl Cl
Cl Cl
H H H H H Zn yellow
116 Cl Cl
Cl Cl
H Cl H H H Ni yellow
117 Cl Cl
Cl Cl
H Cl H H H Cu yellow-green
118 Cl Cl
Cl Cl
H Cl H H H Zn yellow
119 Cl Cl
Cl Cl
H CH.sub.3
H H H Ni yellow-orange
120 Cl Cl
Cl Cl
H CH.sub.3
H H H Cu yellow
121 Cl Cl
Cl Cl
H CH.sub.3
H H H Zn yellow
122 Cl Cl
Cl Cl
H H H Cl
H Ni yellow
123 Cl Cl
Cl Cl
H H H Cl
H Cu yellow-green
124 Cl Cl
Cl Cl
H H H Cl
H Zn yellow
125 Cl Cl
Cl Cl
H H Cl
Cl
H Ni yellow
126 Cl Cl
Cl Cl
H H Cl
Cl
H Cu yellow-green
127 Cl Cl
Cl Cl
H H Cl
Cl
H Zn yellow
128 Cl Cl
OCH.sub.3
Cl
H H H H H Ni yellow
129 Cl Cl
OCH.sub.3
Cl
H H H H H Cu green-yellow
130 Cl Cl
OCH.sub.3
Cl
H Cl H H H Ni yellow
131 Cl Cl
OCH.sub.3
Cl
H Cl H H H Cu yellow-green
132 OCH.sub.3
Cl
OCH.sub.3
Cl
H H H H Ni yellow
133 OCH.sub.3
Cl
OCH.sub.3
Cl
H H H H H Cu yellow
134 OCH.sub.3
Cl
OCH.sub.3
Cl
H CH.sub.3
H H H Ni yellow
greenish-
135 OCH.sub.3
Cl
OCH.sub.3
Cl
H CH.sub.3
H H H Cu tinged yellow
136 OCH.sub.3
Cl
OCH.sub.3
Cl
H Cl H H H Ni yellow
137 Cl Cl
Cl Cl
H H H H CH.sub.3
Ni yellow
138 Cl Cl
Cl Cl
H H H H CH.sub.3
Cu yellow
139 Cl Cl
Cl Cl
H CH.sub.3
H H CH.sub.3
Ni yellow
140 Cl Cl
Cl Cl
H CH.sub.3
H H CH.sub.3
Cu yellow
141 Cl Cl
Cl Cl
H Cl H H CH.sub.3
Ni yellow-brown
142 Cl Cl
Cl Cl
H Cl H H CH.sub.3
Cu yellow-brown
143 OCH.sub.3
Cl
OCH.sub.3
Cl
H H H H CH.sub.3
Ni yellow
144 OCH.sub.3
Cl
OCH.sub.3
Cl
H H H H CH.sub.3
Cu yellow
145 OCH.sub.3
Cl
OCH.sub.3
Cl
H CH.sub.3
H H CH.sub.3
Ni yellow
146 OCH.sub.3
Cl
OCH.sub.3
Cl
H CH.sub.3
H H CH.sub.3
Cu yellow
147 OCH.sub.3
Cl
OCH.sub.3
Cl
H Cl H H CH.sub.3
Ni yellow
148 OCH.sub.3
Cl
OCH.sub.3
Cl
H Cl H H CH.sub.3
Cu yellow
149 OCH.sub.3
Cl
OCH.sub.3
Cl
H Cl H H CH.sub.3
Co yellow-brown
greenish-
150 H H H H H H H H H Ni tinged yellow
greenish-
151 H H H H H H H H H Cu tinged yellow
152 CH.sub.3 O
Cl
OCH.sub.3
Cl
H H Cl
Cl
H Ni yellow
greenish-
153 CH.sub.3 O
Cl
OCH.sub.3
Cl
H H Cl
Cl
H Cu tinged yellow
154 H H H H H H H H CH.sub.3
N yellow
155 H H H H H H H H CH.sub.3
Cu yellow-green
156 H H H H H Cl H H CH.sub.3
N yellow
157 H H H H H Cl H H CH.sub.3
Cu yellow-green
158 Cl Cl
Cl Cl
H H Cl
Cl
CH.sub.3
Ni orange
159 Cl Cl
Cl Cl
H H Cl
Cl
CH.sub.3
Cu yellow
160 Cl Cl
CH.sub.3 O
Cl
H H H H CH.sub.3
Ni yellow
161 Cl Cl
CH.sub.3 O
Cl
H H H H CH.sub.3
Cu yellow
162 Cl Cl
PhO Cl
H H H H H Ni yellow
163 Cl Cl
PhO Cl
H H H H H Cu yellow-green
164 Cl Cl
PhO Cl
H H H H CH.sub.3
Ni yellow
165 Cl Cl
PhO Cl
H H H H CH.sub.3
Cu yellow
166 CH.sub.3 O
Cl
CH.sub.3 O
Cl
H Cl H H CH.sub.3
Ni yellow
167 CH.sub.3 O
Cl
CH.sub.3 O
Cl
H Cl H H CH.sub.3
Cu yellow-green
168 CH.sub.3 O
Cl
CH.sub.3 O
Cl
H H Cl
Cl
H Ni yellow
169 CH.sub.3 O
Cl
CH.sub.3 O
Cl
H H Cl
Cl
H Cu yellow-green
170 CH.sub.3 O
Cl
CH.sub.3 O
Cl
H H Cl
Cl
CH.sub.3
Ni yellow
171 CH.sub.3 O
Cl
CH.sub.3 O
Cl
H H Cl
Cl
CH.sub.3
Cu yellow
__________________________________________________________________________
2.40 g of the bishydrazone of Example 40 are reacted in 60 ml of methylcellosolve with 1.10 g of Cu(ac)2.H2 O for 5 hours at 90° C. The reaction product is filtered off, washed with methylcellosolve and alcohol and dried at 80° C. 2.30 g (85% of theory) are obtained of a yellow-brown pigment of the formula ##STR69## which colours PVC in yellow shades of good fastness to light and migration.
The metal complexes of the formula ##STR70## wherein the symbols have the meaning indicated in Table X which follows, are obtained by an analogous process.
Table X
__________________________________________________________________________
Example
No. X.sub.1
X.sub.2
X.sub.3
X.sub.4
Y.sub.5
Y.sub.6
R.sub.6
M Shade
__________________________________________________________________________
173 Cl Cl Cl Cl H CH.sub.3
Ni yellow
174 Cl Cl Cl Cl H CH.sub.3
Zn yellow
175 Cl Cl Cl Cl Cl CH.sub.3
Ni yellow
176 Cl Cl Cl Cl Cl CH.sub.3
Cu yellow-green
177 OCH.sub.3
Cl OCH.sub.3
Cl H COOC.sub.2 H.sub.5
Ni yellow
178 OCH.sub.3
Cl OCH.sub.3
Cl H COOC.sub.2 H.sub.5
Cu yellow-brown
179 Cl Cl Cl Cl H CH.sub.3
CH.sub.3
Ni yellow
180 Cl Cl Cl Cl H CH.sub.3
CH.sub.3
Cu yellow
181 CH.sub.3 O
Cl CH.sub.3 O
Cl H CH.sub.3
CH.sub.3
Ni yellow
182 CH.sub.3 O
Cl CH.sub.3 O
Cl H CH.sub.3
CH.sub.3
Cu yellow-green
183 CH.sub.3 O
Cl CH.sub.3 O
Cl H H CONH.sub.2
Ni yellow
184 CH.sub.3 O
Cl CH.sub.3 O
Cl H H CONH.sub.2
Cu yellow-green
__________________________________________________________________________
The metal complexes of the following formula ##STR71## wherein the symbols have the meaning indicated in Table XI which follows, are obtained by the methods described above from the bishydrazones of Examples 46 and 47.
Table XI
______________________________________
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
M Shade
______________________________________
185 Cl Cl Cl Cl Ni yellow
186 Cl Cl Cl Cl Cu yellow-green
187 OCH.sub.3
Cl OCH.sub.3
Cl Ni yellow
188 OCH.sub.3
Cl OCH.sub.3
Cl Cu yellow-green
______________________________________
The metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Example 1 with the corresponding metal salts ##STR72##
The following table indicates the meaning of the symbols:
Table XII
______________________________________
Example
No. Y.sub.1 Y.sub.2 Y.sub.3
Y.sub.4
M Shade
______________________________________
189 H H H H Ni yellow
190 H H H H Zn yellow
191 H H H H Cd yellow
192 OC.sub.2 H.sub.5
H H H Ni orange
193 OC.sub.2 H.sub.5
H H H Zn yellow
194 OC.sub.2 H.sub.5
H H H Cd yellow
195 Cl H Cl H Ni brown
196 Cl H Cl H Zn yellow
197 Cl H Cl H Cd yellow
______________________________________
1.50 g of the bishydrazone of Example 48 are heated in 70 ml of methylcellosolve with 0.63 g of Cu(ac)2.H2 O for 3 hours at 100° C. The yellow-green suspension is filtered hot; the filter residue is washed well with methylcellosolve, alcohol and acetone and dried at 80° C. 1.2 g (70% of theory) are obtained of a greenish-tinged yellow pigment of the formula ##STR73##
The procedure is as indicated in Example 198, but the bishydrazone of Example 49 is used as the starting material. The greenish-tinged yellow pigment of the formula ##STR74## is obtained.
1.50 g of the bishydrazone of Example 48 are reacted in 70 ml of methylcellosolve with 0.63 g of Cu(ac)2.H2 O for 3 hours at 100° C. A solution of 1 g of Ba(OH)2.8H2 O in 20 ml of water is run dropwise into this yellow-green suspension. The reaction mixture is heated for a further 2 hours at 100° C and is then filtered hot. The filter residue is washed well with methylcellosolve, water, alcohol and acetone and dried at 90° C. 1.8 g are obtained of a yellow-green pigment which colours PVC in greenish-tinged yellow shades of good fastness to light and migration.
The barium salt of the copper complex of Example 199 is prepared by the process of Example 200. A pigment is obtained which colours PVC in greenish-tinged yellow shades of good fastness to light and migration.
The nickel complex of the same colorant is prepared by the process of Example 200. It colours PVC in yellow shades of good fastness to light and migration.
The metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Examples 56 and 57, with the corresponding metal salts. ##STR75##
The following table indicates the meaning of the symbols.
Table XIII
______________________________________
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
M Shade
______________________________________
203 Cl Cl Cl Cl Ni yellow
204 Cl Cl Cl Cl Cu yellow-green
205 CH.sub.3 O
Cl CH.sub.3 O
Cl Ni yellow
206 CH.sub.3 O
Cl CH.sub.3 O
Cl Cu yellow-green
______________________________________
The metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 58-63 with the corresponding metal salts. ##STR76##
Table XIV
______________________________________
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
R M Shade
______________________________________
207 Cl Cl Cl Cl H Ni yellow
208 Cl Cl Cl Cl H Cu yellow-green
209 Cl Cl CH.sub.3 O
Ci H Ni yellow
210 Cl Cl CH.sub.3 O
Cl H Cu yellow-green
211 CH.sub.3 O
Cl CH.sub.3 O
Cl H Ni yellow
212 CH.sub.3 O
Cl CH.sub.3 O
cl H Cu yellow-green
213 Cl Cl Cl Cl CH.sub.3
Ni yellow
214 Cl Cl Cl Cl CH.sub.3
Cu yellow-green
215 Cl Cl CH.sub.3 O
Cl CH.sub.3
Ni yellow
216 Cl Cl CH.sub.3 O
Cl CH.sub.3
Cu yellow-green
217 CH.sub.3 O
Cl CH.sub.3 O
Cl CH.sub.3
Ni yellow
218 CH.sub.3 O
Cl CH.sub.3 O
Cl CH.sub.3
Cu yellow-green
______________________________________
The metal complexes of the following formula are obtained by reacting the bishydrazones obtained in accordance with Examples 50-55 with the corresponding metal salts. ##STR77##
The following table indicates the meaning of the symbols.
Table XV
______________________________________
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
Y.sub.3
M Shade
______________________________________
219 Cl Cl Cl Cl H Ni yellow
220 Cl Cl Cl Cl H Cu yellow-green
221 CH.sub.3 O
Cl CH.sub.3 O
Cl H Ni yellow
222 CH.sub.3 O
Cl CH.sub.3 O
Cl H Cu yellow-green
223 Cl Cl Cl Cl CH.sub.3 O
Ni yellow
224 Cl Cl Cl Cl CH.sub.3 O
Cu yellow-green
225 CH.sub.3 O
Cl CH.sub.3 O
Cl CH.sub.3 O
Ni yellow
226 CH.sub.3 O
Cl CH.sub.3 O
Cl CH.sub.3 O
Cu yellow-green
227 Cl Cl Cl Cl Cl Ni yellow
228 Cl Cl Cl Cl Cl Cu yellow-green
229 CH.sub.3 O
Cl CH.sub.3 O
Cl Cl Ni yellow
230 CH.sub.3 O
Cl CH.sub.3 O
Cl Cl Cu yellow-green
______________________________________
The metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 64-67 with the corresponding metal salts.
______________________________________
##STR78##
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
R M Shade
______________________________________
231 Cl Cl Cl Cl CN Ni yellow
232 Cl Cl Cl Cl CN Cu yellow
233 CH.sub.3 O
Cl CH.sub.3 O
Cl CN Ni yellow
234 CH.sub.3 O
Cl CH.sub.3 O
Cl CN Cu green-yellow
235 Cl Cl Cl Cl CONH.sub.2
Ni yellow
236 Cl Cl Cl Cl CONH.sub.2
Cu yellow
237 CH.sub.3 O
Cl CH.sub.3 O
Cl CONH.sub.2
Ni yellow
238 CH.sub.3 O
Cl CH.sub.3 O
Cl CONH.sub.2
Cu yellow-green
______________________________________
The metal complexes of the following formula are obtained by reacting the bishydrazones of Examples 68-70 with the corresponding metal salts.
______________________________________
##STR79##
Example
No. X.sub.1 X.sub.2
X.sub.3
X.sub.4
R M Shade
______________________________________
239 Cl Cl Cl Cl CN Ni orange
240 Cl Cl Cl Cl CN Cu yellow
241 CH.sub.3 O
Cl CH.sub.3 O
Cl CN Ni yellow
242 CH.sub.3 O
Cl CH.sub.3 O
Cl CN Cu yellow-green
243 CH.sub.3 O
Cl CH.sub.3 O
Cl CN Co yellow
244 CH.sub.3 O
Cl CH.sub.3 O
Cl CONH.sub.2
Ni yellow
245 CH.sub.3 O
Cl CH.sub.3 O
Cl CONH.sub.2
Cu brown
______________________________________
The metal complexes of the following formula are obtained by reacting the bishydrazones of the Examples under 1 with the corresponding metal salts.
______________________________________
##STR80##
Ex.
No. X.sub.1 X.sub.2
X.sub.3
X.sub. R
M Shade
______________________________________
246 Cl Cl Cl Cl H Ni red-
brown
247 Cl Cl Cl Cl H Cu brown
248 Cl Cl CH.sub.3 O
Cl H Ni red-
brown
249 Cl Cl CH.sub.3 O
Cl H Cu yellow-
brown
250 CH.sub.3 O
Cl CH.sub.3 O
Cl H Ni yellow-
brown
251 CH.sub.3 O
Cl CH.sub.3 O
Cl H Cu yellow
252 Cl Cl Cl Cl CH.sub.3 Ni red-
brown
253 Cl Cl Cl Cl CH.sub.3 Cu brown
254 Cl Cl CH.sub.3 O
Cl CH.sub.3 Ni red-
brown
255 Cl Cl CH.sub.3 O
Cl CH.sub.3 Cu brown
256 CH.sub.3 O
Cl CH.sub.3 O
Cl CH.sub.3 Ni red-
brown
257 CH.sub.3 O
Cl CH.sub.3 O
Cl CH.sub.3 Cu yellow-
brown
258 Cl Cl Cl Cl
##STR81## Ni red
259 Cl Cl Cl Cl
##STR82## Cu orange
260 Cl Cl CH.sub.3 O
Cl
##STR83## Ni red
261 Cl Cl CH.sub.3 O
Cl
##STR84## Cu orange
262 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR85## Ni red- brown
263 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR86## Cu yellow- brown
264 Cl Cl Cl Cl
##STR87## Ni red
265 Cl Cl Cl Cl
##STR88## Cu yellow- orange
266 Cl Cl CH.sub.3 O
Cl
##STR89## Ni red- brown
267 Cl Cl CH.sub.3 O
Cl
##STR90## Cu yellow- brown
268 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR91## Ni red- brown
269 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR92## Cu yellow- brown
270 Cl Cl Cl Cl
##STR93## Ni red
271 Cl Cl Cl Cl
##STR94## Cu red- brown
272 Cl Cl CH.sub.3 O
Cl
##STR95## Ni red- brown
273 Cl Cl CH.sub.3 O
Cl
##STR96## Cu yellow- brown
274 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR97## Ni red- brown
275 CH.sub.3 O
Cl CH.sub.3 O
Cl
##STR98## Cu yellow- brown
276 Cl Cl Cl Cl
##STR99## Ni red
277 Cl Cl Cl Cl
##STR100## Cu red- brown
______________________________________
All the metal complexes described can also be prepared directly from the components, isoindolinone-3-ylidene hydrazine, hydroxy-aldehyde or hydroxy-ketone and metal salt by the one-pot method.
1.45 g of 5,7-dichloro-4,6-dimethoxy-isoindolin-1-on-3-ylidene hydrazine, 0.945 g of 2,4-dihydroxyquinoline-3-aldehyde and 1.25 g of Ni(ac)2.4H2 O are reacted for 1 hour at 100° C in 50 ml of glacial acetic acid. The yellow-orange suspension is filtered at 80° C, washed well with glacial acetic acid, alcohol and acetone and dried at 80° C. 2.40 g (93% of theory) of a yellow pigment, identical with the product of Example 132, are obtained.
The formation of the metal complex can also be carried out in, for example, dimethylformamide, methylcellosolve, ethylcellosolve, Carbitol and glycol, instead of glacial acetic acid.
65 parts of stabilised polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 part of the colorant obtained in accordance with Example 89 are stirred together with one another and are then worked for 7 minutes at 140° C on a twin-roll calender. An orange sheet of very good fastness to light and migration is obtained.
1.00 g of the pigment prepared according to Example 113 is finely ground on an Engelsmann grinding machine together with 4.00 g of printer's varnish of the following composition:
______________________________________
29.4% of linseed oil-stand oil
(300 poises),
67.2% of linseed oil-stand oil
(20 poises),
2.1% of cobalt octoate
(8% of Co) and
1.3% of lead octoate (24% of Pb)
______________________________________
and is then printed on art printing paper at 1 g/m2 in the letterpress process with the aid of a block. A strong, pure shade of yellow, having good transparency and good gloss, is obtained. Very brilliant green shades can be produced in three- or four-colour printing by overprinting on blue.
The pigment is also suitable for other printing processes, such as gravure printing, offset printing and flexographic printing, and here too gives very good results.
Claims (8)
1. Azomethine pigments of the formula ##STR101## and metal complexes thereof, wherein A denotes an isocyclic or heterocyclic aromatic radical, R denotes a H atom, X2 and X4 denote H atoms or halogen atoms, X1 and X3 denote H atoms or halogen atoms, alkoxy or alkylmercapto groups containing 1-6 C atoms, cycloalkoxy groups containing 5-6 C atoms, or aralkoxy, aryloxy or arylmercapto groups, it being possible for one of the substituents X1 -X4 also to be a nitro group.
2. Azomethine pigments according to claim 1, of the formula ##STR102## wherein M denotes a divalent metal atom and A, R and X1 -X4 have the meaning indicated in claim 1.
3. Azomethine pigments according to claim 2, of the formula ##STR103## wherein A1 denotes a benzene, pyridine, pyrimidine, or pyrane radical which can also contain a fused benzene nucleus, or denotes a pyrazolone radical, R1 denotes a hydrogen atom, M1 denotes a copper or nickel atom, X5 and X7 denote H atoms or chlorine atoms or alkoxy groups containing 1-4 C atoms, and X6 and X8 denote H atoms or chlorine atoms, X6 and X8 representing chlorine atoms if X5 and X7 denote alkoxy groups.
4. Azomethine pigments according to claim 3, of the formula ##STR104## wherein R1, M1 and X5 to X8 have the meaning indicated in claim 3, Y3 and Y4 denote H atoms or halogen atoms, alkyl or alkoxy groups containing 1-4 C atoms, nitro groups or groups of the formula ##EQU5## wherein M2 denotes a Ca, Sr, Ba or Mn atom, and Z represents an O atom or an imino group.
5. Azomethine pigments according to claim 4, of the formula ##STR105## wherein R1, M1, X5 to X8, Y3 and Y4 have the meaning indicated in claims 3 and 4.
6. Azomethine pigments according to claim 3, of the formula ##STR106## wherein M1 and X5 to X8 have the meaning indicated in claim 3, and R3 denotes nitrile or a carbamoyl group.
7. Azomethine pigments according to claim 3, of the formula ##STR107## wherein M1 and X5 to X8 have the meaning indicated in claim 3, and R4 denotes nitrile or a carbamoyl group.
8. Azomethine pigments according to claim 3, of the formula ##STR108## wherein M1 and X5 to X8 have the meaning indicated in claim 3, and R5 denotes a hydrogen atom or a lower alkyl group or an aryl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/693,388 US4024132A (en) | 1973-09-07 | 1976-06-07 | Azomethine pigments |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1288973A CH581683A5 (en) | 1973-09-07 | 1973-09-07 | |
| US05/693,388 US4024132A (en) | 1973-09-07 | 1976-06-07 | Azomethine pigments |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/502,246 Division US3974149A (en) | 1973-09-07 | 1974-08-30 | Azomethine pigments |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4024132A true US4024132A (en) | 1977-05-17 |
Family
ID=25711171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/693,388 Expired - Lifetime US4024132A (en) | 1973-09-07 | 1976-06-07 | Azomethine pigments |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4024132A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234586A (en) * | 1977-12-29 | 1980-11-18 | Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara Rt. | Nitrogen bridgehead compounds having anti-allergic effect |
| FR2455582A1 (en) * | 1979-05-02 | 1980-11-28 | Sandoz Sa | NOVEL 2,5-DIIMINO-PYRROLINES, THEIR PREPARATION AND THEIR USE AS PIGMENTS |
| EP0020299A1 (en) * | 1979-05-23 | 1980-12-10 | Ciba-Geigy Ag | Nickel complexes of azines, their preparation process, pigmenting process for a high molecular organic material and the material so obtained |
| US4349671A (en) * | 1980-03-13 | 1982-09-14 | Ciba-Geigy Corporation | Process for the production of metal complexes of isoindoline azines |
| US4366312A (en) * | 1980-03-13 | 1982-12-28 | Ciba-Geigy Corporation | Metal complexes of isoindolinazines, process for their preparation and use |
| US5523027A (en) * | 1993-08-27 | 1996-06-04 | Orient Chemical Industries, Ltd. | Long-wavelength UV light absorber |
| US6180788B1 (en) * | 1997-12-16 | 2001-01-30 | Exxon Research And Engineering Company | Catalyst compositions |
| EP1516895A1 (en) * | 2003-09-19 | 2005-03-23 | Clariant International Ltd. | New coumarin type dyes for optical data recording |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3867404A (en) * | 1972-01-17 | 1975-02-18 | Ciba Geigy Corp | New isoindolinone pigments and process for their manufacture |
| US3896113A (en) * | 1971-12-31 | 1975-07-22 | Sandoz Ltd | Novel metallized heterocyclic derivatives |
-
1976
- 1976-06-07 US US05/693,388 patent/US4024132A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3896113A (en) * | 1971-12-31 | 1975-07-22 | Sandoz Ltd | Novel metallized heterocyclic derivatives |
| US3867404A (en) * | 1972-01-17 | 1975-02-18 | Ciba Geigy Corp | New isoindolinone pigments and process for their manufacture |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234586A (en) * | 1977-12-29 | 1980-11-18 | Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara Rt. | Nitrogen bridgehead compounds having anti-allergic effect |
| US4461769A (en) * | 1977-12-29 | 1984-07-24 | Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara R.T. | Nitrogen bridgehead compounds having anti-allergic effect |
| FR2455582A1 (en) * | 1979-05-02 | 1980-11-28 | Sandoz Sa | NOVEL 2,5-DIIMINO-PYRROLINES, THEIR PREPARATION AND THEIR USE AS PIGMENTS |
| EP0020299A1 (en) * | 1979-05-23 | 1980-12-10 | Ciba-Geigy Ag | Nickel complexes of azines, their preparation process, pigmenting process for a high molecular organic material and the material so obtained |
| US4355159A (en) * | 1979-05-23 | 1982-10-19 | Ciba-Geigy Corporation | Nickel complex pigments of azines |
| US4460768A (en) * | 1979-05-23 | 1984-07-17 | Ciba-Geigy Corporation | Nickel complex pigments of azines |
| US4349671A (en) * | 1980-03-13 | 1982-09-14 | Ciba-Geigy Corporation | Process for the production of metal complexes of isoindoline azines |
| US4366312A (en) * | 1980-03-13 | 1982-12-28 | Ciba-Geigy Corporation | Metal complexes of isoindolinazines, process for their preparation and use |
| US5523027A (en) * | 1993-08-27 | 1996-06-04 | Orient Chemical Industries, Ltd. | Long-wavelength UV light absorber |
| US6180788B1 (en) * | 1997-12-16 | 2001-01-30 | Exxon Research And Engineering Company | Catalyst compositions |
| EP1516895A1 (en) * | 2003-09-19 | 2005-03-23 | Clariant International Ltd. | New coumarin type dyes for optical data recording |
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